Process for making finely divided silica



U ITED STARS PROCESS FOR MAKING FINELY DIVIDED SILICA Paul S. Moyer, deceased, late of Lake Forest, 11]., by Elizabeth F. Moyer, administratrix, Lake Forest, 1]].

No Drawing. Application October 25, 1941, Serial No. 416,582

10 Claims. (Cl. 23-182) The present invention relates to an improved in which, however, the sodium is still united with process for the manufacture of extremely finely the silicic acid component. The suspension is divided silica from such materials as the alkali then neutralized until it is faintly acid. This silicates, and the product thus made. Primarily may be accomplished by any suitable acid-reactthe process involves the conversion of an aqueous 5 ing material, or organic or mineral acid, but prefalkali silicate solution into particles of free silicic erably is accomplished by passing carbon dioxide acid, or silica, by the expedient of admixing the gas into and through the mixture. The bubbling solution with a considerable volume of a waterof the carbon dioxide gas also serves as a means miscible organic liquid such as a ketone, alcohol, of agitating the mixture. The acid-reacting subor the like, which has the effect of throwing the stance used will unite with the sodium component silicate out of solution in the form of fine parof the silicate, forming the corresponding sodium ticles of the alkali silicate. salt. In the case of carbon dioxide, it will obvi- The resulting suspension of particles is then ously be sodium carbonate; and, as suflicient carneutralized with an acid-reacting material so as bon dioxide is used to produce a faintly acid reto produce the free silicic acid, or silica, while at action, most of the sodium carbonate will have the same time forming a solution of the sodium been changed over into bicarbonate. The resultsalt of the particular acid-reacting material emg suspension of free silica, then probably in the ployed. The silica thus produced is then filtered form of silicic acid, is filtered or otherwise treated off, washed substantially free from water-soluble to recover therefrom the free silicic acid particles, material, and then dried. The dry product may, which are then washed, preferably by means of if desired, be lightly ground in order to re-sepaa mixture of methanol and water, having about rate it into its constituent particulate form in the same relative proportions of alcohol and Case there has been any formation of aggregates water as have been present in the mixture of the of particles into lumps. silicate solution and the alcohol. The reason for The material produced is characterized by being this is to av i if p l r lution of silicic in such finely divided form that the particles in acid o silica during the w hin p i n. The most a e r not, m h larger th 11) or 15 resulting filter cake, if filtration has been used microns and in any event very much smaller than as a sep eans, is then dried and may he could b obtained by th grinding of ordinary lightly ground or separated back into its original silica, rock, or sand. Moreover, the particles are particles. substantially globular and free from sharp edges The fi te as l as the s q are and are hence desirable if the product is to be billed, thus producing an q ous soluti n of, in used as a filler in paints or enamels, for example this case, sodium carbonate and bicarbonate and as a base for application to metallic plates to 3, alcohol. This solution is then fractionall diswhich lithographing or printing is to be applied. tilled to recover from it the therein contained As a more particular example of the method methanol, which of course may be re-used imof carrying out the present invention, for example, mediately in t further C y ut f th a solution of sodium silicate may be prepared, P s-411M is to say, for the treatment of furcontaining approximately 10% of sodium silicate, ther batches of silicate solution. The residue in which may be any of the commercially available the still, containing the sodium carbonate and forms of this commodity, but most advantabicarbonate, is then evaporated to dryness, thus geously is in the form of water-glass. recovering the sodium salts. They either may be A solution of sodium silicate containing about sold or, quite advantageously, may be mixed with 10% of total solids-such as may, for instance. be n pp p at a t of Si as example produced by diluting 190 grams of a 38% solution a high silica sand, and heated therewith to gentle of sodium silicate with 800 c. c. of hot water, so fusion, thereby producing a new supply of sodium adjusted that the mixture will have a, temperasilicate. As a result of the reaction between the ture of about 130 F.-may be poured into a mixsodium carbonate and bicarbonate with the silica,

ture of 800 c. c. of methyl alcohol (methanol) and 5 carbon dioxide will be liberated and thus may be 100 c. c. of water. The alcohol solution should employed for the further carrying out of the be rapidly stirred as the sodium silicate solution process. This gas may be stored to form a supply is introduced, the result being the separation of which may be passed into a subsequently made very finely divided globular particles of sodium new suspension of sodium silicate particles in a silicate. This forms a sort of creamy suspension mixture of methanol and water.

It will be seen that by this expedient a complete cyclic process will eventuate in which, starting with sodium carbonate and sand, extremely finely divided silica can be produced. The only ingredient thus used up will be the sand or other source of silica, while the alcohol and the sodium salt, i. e., the carbonate, are continually regenerated in the process.

If instead of carbon dioxide, hydrochloric acid, for example, is employed, this will, of course, form sodium chloride, which will be in the residue 01' the distillation of the alcohol. This sodium chloride can also be melted with sand, forming sodium silicate, while liberating hydrochloric acid, which may then be re-used in the process.

However, the process is not limited to a cyclic operation, and therefore other acids or acidreacting substances may be employed for the purpose of removing the sodium component of the finely divided precipitated silica.

While the process has been described in connection with sodium silicate and methanol, it will be obvious to any experienced chemist that it can be practiced, with substantially the same results, by starting out with potassium silicate. Furthermore, the methanol employed for precipitating the alkali silicate solution may be replaced by equivalent materials, such as other alcohols of the aliphatic series such as ethyl alcohol (ethanol), propyl or isopropyl alcohol, or some other water-soluble or water-miscible organic liquid such as acetone, ethyl-methyl ketone, and the like. However, methanol is probably the least expensive and most easily procurable of these materials, and hence is the preferred substance for the carrying out of the present invention.

The product,'in addition to the uses already given for it, also forms an excellent filler or pigment which may be used in paper coating compositions and the like.

Obvious modifications of the process herein disclosed, such as those which will occur to any skilled chemist, are to be construed as within the scope of the present invention, for which is claimed:

1. Process of preparing very finely divided silica which comprises mixing an aqueous solution of an alkali silicate with a water-miscible organic liquid non-reactive therewith, thereby precipitating said silicate in finely divided form, and acidulating the suspension to form free silica, separating the latter from the liquid, and drying the same.

2. Process of preparing very finely divided silica which comprises mixing an aqueous solution oi an alkali silicate with a water-miscible organic liquid non-reactive therewith, acidulating the mixture, separating the thug iormed free silica from the liquid, and drying the same.

3. Process 01' preparing very finely divided silica which comprises mixing an aqueous solution or an alkali silicate with a water-miscible organic liquid non-reactive therewith, passing carbon dioxide gas into the resulting mixture until it has been substantially neutralized, separating the thus formed tree silica from the liquid, and drying the same.

4. Process oi. preparing very finely divided silica which comprises mixing an aqueous solufrom soluble material, and drying the silica particles thus obtained.

6. The process of claim 5, in which the acidreacting-substance is carbonic acid.

7. Cyclic process of producing very finely divided silica which comprises dissolving sodium silicate in water to form a solution, pouring the latter into a substantial volume 'of a watermiscible organic liquid non-reactive therewith to precipitate said silicate in finely divided form, passing carbon dioxide into the suspension to form free silica and sodium carbonate, separating the silica from the liquid in which it is sus- 40 pended, washing and drying it, collecting the filtrate and wash-liquor, distilling the organic liquid therefrom for re-use, recovering the sodium carbonate from the residual liquid and heating the same with silica to form sodium silicateand carbon dioxide, dissolving the former to form a sodium silicate solution, pouring the latter into the recovered organic liquid and passing the carbon dioxide into the suspension.

8. The process of claim '7, in which the organic liquid is an alcohol.

9. The process of claim '1, in which the organic liquid is a ketone.

10. The process of claim '7, in which the organic liquid is methanol.

ELIZABETH F. MOYER, Administratria: of the Estate of Paul S. Mayer,

Deceased. 

